Porous α-Fe 2 O 3 hollow microspheres were synthesized through a simple and efficient carbon sphere template method. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and N 2 adsorption–desorption. Structural characterization indicated that as-prepared α-Fe 2 O 3 hollow microspheres had porous structure with around 200nm in diameter and thin shell about 10nm thick. The average pore size and Brunauer–Emmett–Teller specific surface area of α-Fe 2 O 3 hollow microspheres were 6.5nm and 111.6m 2 /g, respectively. The gas sensing behavior investigation showed that as-synthesized α-Fe 2 O 3 hollow microspheres exhibited very good gas sensing property to acetone vapor.